Tower type solar thermo-chemical ammonia production system and ammonia production method

Abstract

The application discloses a tower type solar thermochemical ammonia production system and ammonia production method, wherein sunlight is reflected to a solar heat collection tower by a heliostat field for heat collection; the solar heat collection tower is connected with all reaction kettles and a CO reactor for providing heat required by reactions; the CO reactor, a catalyst sample tank and a water vapor storage tank are all connected with all reaction kettles; in the reaction kettles, high-valence metal oxides delivered by the catalyst sample tank are first subjected to a reduction reaction with CO, and then low-valence metal oxides are subjected to a cracking reaction with water vapor to obtain hydrogen; nitrogen and hydrogen enter an ammonia reaction device for an ammonia synthesis reaction to produce ammonia. The application uses solar light heat as a heat source and cracks water to produce hydrogen through a cyclic oxidation-reduction reaction, and further synthesizes ammonia, thereby reducing the production energy consumption and production cost of the synthesized ammonia, and realizing environment-friendly, efficient and recyclable ammonia synthesis.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ammonia synthesis, in particular to a tower type solar thermo-chemical ammonia synthesis system and method. BACKGROUND

[0002] Ammonia is a multifunctional compound, which is used as raw material for nitrogen fertilizer industry, organic synthesis industry, and manufacturing of nitric acid, ammonium salt and soda ash, and is also a commonly used refrigerant, and the domestic market has a huge demand for it. In addition, ammonia energy, as a new type of energy with environmental protection, high energy density, high safety, low transportation and storage cost, can be directly used as a hydrogen-rich fuel, and can also be used as an energy carrier of hydrogen, and has a broad development prospect in the fields of ammonia-hydrogen, ammonia-electricity.

[0003] At present, the synthesis process of ammonia mainly uses coal as raw material, generates hydrogen through coal gas, and synthesizes ammonia by reacting with nitrogen under high temperature (300-500 DEG C) and high pressure (20.26-30.39 MPa), but the process has problems of high energy consumption, high CO2 emission and high production cost. SUMMARY

[0004] In view of the problems in the prior art, the present application provides a tower type solar thermo-chemical ammonia synthesis system and method, which uses solar light heat as a heat source and cracks water to obtain hydrogen through a cyclic oxidation-reduction reaction, and further synthesizes ammonia, thereby reducing the production energy consumption and production cost of ammonia synthesis, and realizing environmentally friendly, efficient and recyclable ammonia synthesis.

[0005] The present application discloses a tower type solar thermo-chemical ammonia synthesis system, which comprises a tower type solar heat collection module, a light-heat reaction module and an ammonia synthesis module.

[0006] The tower type solar heat collection module comprises a heliostat field and a solar heat collection tower, the heliostat field reflects sunlight to the solar heat collection tower, and converts collected solar energy into heat energy.

[0007] The photo-thermal reaction module comprises at least one reaction kettle, a CO reactor, a catalyst sample tank and a water vapor storage tank, the solar heat collection tower is connected with all the reaction kettles and the CO reactor for providing heat required by the reaction; the CO reactor is connected with all the reaction kettles through a first pressure pump, the catalyst sample tank is connected with all the reaction kettles through a powder particle solid feeder, and the water vapor storage tank is connected with all the reaction kettles through a second pressure pump; wherein, in the reaction kettle, the high-valence metal oxide delivered by the catalyst sample tank is first subjected to a reduction reaction with CO delivered by the CO reactor to obtain low-valence metal oxide and CO2, and the CO2 returns to the CO reactor to react with carbon material to generate CO again; then, the low-valence metal oxide is subjected to a cracking reaction with water vapor delivered by the water vapor storage tank to obtain high-valence metal oxide and hydrogen.

[0008] The ammonia production module comprises an ammonia reaction device and an ammonia collection device, nitrogen and hydrogen produced by the photo-thermal reaction module enter the ammonia reaction device to perform a synthetic ammonia reaction, and the produced ammonia gas is delivered to the ammonia collection device.

[0009] As a further improvement of the present application, the number of reaction kettles is two, which are a first reaction kettle and a second reaction kettle, and the first reaction kettle and the second reaction kettle are arranged side by side.

[0010] As a further improvement of the present application, the heliostat field is composed of a plurality of heliostats arranged around the solar heat collection tower, the heliostat field focuses sunlight onto the solar heat collection tower, the temperature of the solar heat collection tower is controlled by adjusting the height and angle of the heliostats, thereby controlling the heating temperature of the reaction kettle and the CO reactor; the reaction kettle can be a solid bed reactor or a boiling bed reactor, and is internally provided with a stirring device.

[0011] As a further improvement of the present application, the high-valence metal oxide is a cage oxide, preferably Fe3O4; the low-valence metal oxide is FeO, and the average particle size of the high-valence metal oxide and the low-valence metal oxide is between 5-100 um.

[0012] As a further improvement of the present application, in the reaction kettle:

[0013] The reaction temperature of the reduction reaction is 680-710 DEG C, and the chemical reaction equation is:

[0014] Fe3O4+CO=FeO+CO2;

[0015] The reaction temperature of the cracking reaction is 1000-1400 DEG C, and the chemical reaction equation is:

[0016] FeO+H2O(l)=Fe3O4+H2。

[0017] As a further improvement of the present application, the photo-thermal reaction module further comprises: a first condenser, a hydrogen membrane separator, a waste gas storage tank and a hydrogen storage tank.

[0018] The gas outlet of the reaction kettle is connected with a first condenser, which is used to remove water vapor in high-temperature mixed gas containing hydrogen, and the removed water vapor is transported to the water vapor storage tank through a third pressure pump, and the remaining gas after removing the water vapor enters the hydrogen membrane separator; the purified hydrogen separated through the hydrogen membrane separator is stored in the hydrogen storage tank, and the waste gas after separating the hydrogen is stored in the waste gas storage tank; the hydrogen storage tank is connected with the ammonia reaction device.

[0019] As a further improvement of the present application, the ammonia production module further comprises: a second condenser; the second condenser is arranged between the ammonia reaction device and the ammonia collection device, and is used to reduce the temperature of the generated ammonia gas, facilitating collection.

[0020] The application also discloses a tower type solar energy thermo-chemical ammonia production method, which comprises the following steps:

[0021] Step 1: at the beginning, all valves are in a closed state, high-valence metal oxides as catalysts are added into a reaction kettle through a powder particle solid feeder, and are uniformly stirred to be dispersed; a first pressure pump is opened, CO gas is introduced into the reaction kettle through a CO reactor, the temperature of the reaction kettle is controlled to be 680-710 DEG C, a reduction reaction occurs, the reaction time is 30-60 min, and after the reaction is completed, CO2 generated is collected back to the CO reactor, and the CO2 reacts with carbon materials in the CO reactor to generate CO again;

[0022] Step 2: the first pressure pump is closed, a second pressure pump is opened, water vapor is introduced into the reaction kettle, the temperature of the reaction kettle is controlled to be 1000-1400 DEG C, a cracking reaction occurs, the reaction time is 30-60 min, high-valence metal oxides and hydrogen gas are obtained;

[0023] Step 3: nitrogen and hydrogen gas obtained through the cracking reaction in step 2 are added into an ammonia reaction device, the temperature of the ammonia reaction device is controlled to be 400-500 DEG C, a synthesis ammonia reaction occurs, the reaction time is 30-60 min, and ammonia gas generated in the reaction is collected in an ammonia collection device.

[0024] As a further improvement of the present application, in the step 1,

[0025] CO2 and carbon materials in the CO reactor react at 600-800 DEG C to generate CO again, realizing recycling of CO.

[0026] As a further improvement of the present application, in the step 2,

[0027] The mixed gas containing hydrogen generated by the cracking reaction is first cooled by a first condenser to remove excess water vapor, the removed water vapor is transported to the water vapor storage tank by a third pressure pump, and the remaining gas after removal of the water vapor enters the hydrogen membrane separator; the purified hydrogen separated by the hydrogen membrane separator is stored in the hydrogen storage tank, the waste gas after separation of the hydrogen is stored in the waste gas storage tank, and the hydrogen in the hydrogen storage tank is transported to the ammonia reaction device.

[0028] As a further improvement of the present application, in the step 3,

[0029] The ammonia gas generated by the reaction is cooled by a second condenser, the remaining gas is discharged after treatment, and the ammonia gas is collected by an ammonia collecting device.

[0030] Compared with the prior art, the present application has the following beneficial effects:

[0031] 1. The present application adopts a chemical cycle heat mode, the metal oxide is continuously recycled in the reaction kettle, and the consumed raw materials are only carbon substances, water and nitrogen, so the process cost is low;

[0032] 2. The present application uses solar energy as a heat source, uses a solar heat collection tower to convert collected solar energy into heat energy, provides the required heat for the reduction reaction and cracking reaction of the reaction kettle and the preparation of CO in the CO reactor, converts the heat energy into chemical energy, and reduces the process energy consumption of the entire ammonia production system;

[0033] 3. The present application collects CO2 generated by the reduction reaction in the reaction kettle into the CO reactor to further generate CO, and almost no CO2 emission is generated;

[0034] 4. The present application has high energy utilization efficiency, reduces the waste of exhaust heat, and obtains high ammonia production efficiency. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figure 1 The present application discloses a tower type solar thermal chemical ammonia production system.

[0036] In the figure:

[0037] 1 - heliostat field, 2 - solar heat collection tower, 3 - first reaction kettle, 4 - second reaction kettle, 5 - catalyst sample tank, 6 - powder particle solid feeder, 7 - water vapor storage tank, 8 - first pressure pump, 9 - second pressure pump, 10 - first condenser, 11 - hydrogen membrane separator, 12 - waste gas storage tank, 13 - hydrogen storage tank, 14 - ammonia reaction device, 15 - second condenser, 16 - ammonia collecting device, 17 - CO reactor, 18 - third pressure pump. DETAILED DESCRIPTION

[0038] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0039] The present invention will now be described in further detail with reference to the accompanying drawings:

[0040] like Figure 1 As shown, this invention provides a tower-type solar thermochemical ammonia production system, comprising: a tower-type solar collector module, a photothermal reaction module, and an ammonia production module; wherein,

[0041] The tower-type solar thermal collector module of the present invention includes a heliostat field 1 and a solar thermal collector tower 2. The heliostat field 1 is composed of multiple heliostats surrounding the solar thermal collector tower 2. The heliostat field 1 focuses sunlight onto the solar thermal collector tower 2. The temperature of the solar thermal collector tower 2 is controlled by adjusting the height and angle of the heliostats to convert the collected solar energy into heat energy, thereby controlling the heating temperature of the first reactor 3, the second reactor 4 and the CO reactor 17.

[0042] The photothermal reaction module of the application comprises a No. 1 reaction kettle 3, a No. 2 reaction kettle 4, a catalyst sample tank 5, a powder particle solid feeder 6, a water vapor storage tank 7, a No. 1 pressure pump 8, a No. 2 pressure pump 9, a No. 1 condenser 10, a hydrogen membrane separator 11, a waste gas storage tank 12, a hydrogen storage tank 13, a CO reactor 17 and a No. 3 pressure pump 18; the solar heat collection tower 2 is connected with the No. 1 reaction kettle 3, the No. 2 reaction kettle 4 and the CO reactor 17, and is used to provide the temperature required for reduction, cracking and other reactions; the CO reactor 17 is connected with the No. 1 reaction kettle 3 and the No. 2 reaction kettle 4 through the No. 1 pressure pump 8, and is used to transport CO into the No. 1 reaction kettle 3 and the No. 2 reaction kettle 4 to carry out reduction reaction; the catalyst sample tank 5 is connected with the No. 1 reaction kettle 3 and the No. 2 reaction kettle 4 through the powder particle solid feeder 6, and is used to transport high-valence metal oxide used for reduction reaction into the No. 1 reaction kettle 3 and the No. 2 reaction kettle 4, wherein the high-valence metal oxide is cage oxide, and preferably Fe3O4; the water vapor storage tank 7 is connected with the No. 1 reaction kettle 3 and the No. 2 reaction kettle 4 through the No. 2 pressure pump 9, and is used to transport water vapor used for cracking reaction into the No. 1 reaction kettle 3 and the No. 2 reaction kettle 4. Specifically, in the No. 1 reaction kettle 3 and the No. 2 reaction kettle 4, the high-valence metal oxide first carries out reduction reaction with CO to obtain low-valence metal oxide FeO and CO2, and the CO2 returns to the CO reactor to react with carbon material at 600-800℃ to generate CO again, so as to realize recycling of CO; then, the low-valence metal oxide FeO carries out cracking reaction with water vapor to obtain high-valence metal oxide and hydrogen. A No. 1 condenser 10 is connected to the gas outlet of the No. 1 reaction kettle 3 and the No. 2 reaction kettle 4, and is used to remove water vapor in high-temperature mixed gas containing hydrogen; the removed water vapor is transported to the water vapor storage tank 7 through the No. 3 pressure pump 18; the remaining gas after removal of water vapor enters the hydrogen membrane separator 11; the purified hydrogen separated through the hydrogen membrane separator 11 is stored in the hydrogen storage tank 13; and the waste gas after separation of hydrogen is stored in the waste gas storage tank 12.

[0043] The reaction temperature of the reduction reaction is 680-710℃, and the chemical reaction equation is:

[0044] Fe3O4+CO=FeO+CO2;

[0045] The reaction temperature of the cracking reaction is 1000-1400℃, and the chemical reaction equation is:

[0046] FeO+H2O(l)=Fe3O4+H2.

[0047] Further, the No. 1 reaction kettle 3 and the No. 2 reaction kettle 4 can be solid bed reactors or ebullated bed reactors, and are internally provided with stirring devices; the average particle size of the high-valence metal oxide and the low-valence metal oxide is between 5-100um.

[0048] The ammonia production module comprises, in sequence, an ammonia reaction device 14, a second condenser 15 and an ammonia collecting device 16, the hydrogen storage tank 13 is connected with the ammonia reaction device 14, the hydrogen in the nitrogen and hydrogen storage tank 13 enters the ammonia reaction device 14 to carry out synthetic ammonia reaction, the ammonia gas generated by the reaction is cooled by the second condenser 15, the remaining gas is treated and discharged, and the ammonia gas is collected by the ammonia collecting device 16.

[0049] The application provides a tower type solar energy thermochemical ammonia production method, which comprises the following steps:

[0050] Step 1: at the beginning, the valves are all in the closed state, Fe3O4 in the catalyst sample tank 5 as a catalyst is added into the first reaction kettle 3 and the second reaction kettle 4 through the powder particle solid feeder 6, and is uniformly stirred to be dispersed; the first pressure pump 8 is opened, CO gas is introduced into the first reaction kettle 3 and the second reaction kettle 4 through the CO reactor 17, the temperature of the first reaction kettle 3 and the second reaction kettle 4 is controlled to be 680-710 DEG C through the solar heat collection tower 2, a reduction reaction occurs, the reaction time is 30-60 min, low-valence metal oxide FeO and CO2 are obtained; after the reaction is completed, the generated CO2 is collected back to the CO reactor 17, the CO2 and the carbon material in the CO reactor 17 react again to generate CO at 600-800 DEG C, and the recycling of CO is realized;

[0051] Step 2: the first pressure pump 8 is closed, the second pressure pump 9 is opened, the water vapor in the water vapor storage tank 7 is introduced into the first reaction kettle 3 and the second reaction kettle 4, the temperature in the first reaction kettle 3 and the second reaction kettle 4 is controlled to be 1000-1400 DEG C, the low-valence metal oxide FeO and the water vapor carry out a cracking reaction, the reaction time is 30-60 min, Fe3O4, hydrogen and other gases are obtained; the mixed gas containing hydrogen generated by the cracking reaction is first cooled to remove excess water vapor through the first condenser 10, the removed water vapor is transported to the water vapor storage tank 7 through the third pressure pump 18, the remaining gas after the removal of water vapor enters the hydrogen membrane separator 11; the purified hydrogen separated through the hydrogen membrane separator 11 is stored in the hydrogen storage tank 13, and the waste gas after the separation of hydrogen is stored in the waste gas storage tank 12;

[0052] Step 3: the hydrogen in the nitrogen and hydrogen storage tank 13 is added into the ammonia reaction device 14, the temperature of the ammonia reaction device is controlled to be 400-500 DEG C, a synthetic ammonia reaction occurs, the reaction time is 30-60 min; the ammonia gas generated by the reaction is cooled through the second condenser 15, the remaining gas is treated and discharged, the ammonia gas is collected through the ammonia collecting device 16, so that the purpose of low energy consumption, low cost and high yield for ammonia production is realized.

[0053] Example 1:

[0054] A tower type solar energy thermo-chemical ammonia production system and method, the catalyst uses metal oxide, the metal oxide and CO occurs reduction reaction, generates low valence metal oxide, the reaction temperature is 680 DEG C, the reaction time is 30 minutes. Low valence metal oxide and water vapor occur cracking reaction, regenerate high valence metal oxide and hydrogen, the reaction temperature is 1000 DEG C, the reaction time is 30 minutes, hydrogen occurs synthetic ammonia reaction with nitrogen in ammonia reaction device, generates ammonia, the reaction temperature is 400 DEG C, the reaction time is 30 minutes.

[0055] Example 2:

[0056] A tower type solar energy thermo-chemical ammonia production system and method, the catalyst uses metal oxide, the metal oxide and CO occurs reduction reaction, generates low valence metal oxide, the reaction temperature is 690 DEG C, the reaction time is 40 minutes. Low valence metal oxide and water vapor occur cracking reaction, regenerate high valence metal oxide and hydrogen, the reaction temperature is 1100 DEG C, the reaction time is 40 minutes, hydrogen occurs synthetic ammonia reaction with nitrogen in ammonia reaction device, generates ammonia, the reaction temperature is 430 DEG C, the reaction time is 40 minutes.

[0057] Example 3:

[0058] A tower type solar energy thermo-chemical ammonia production system and method, the catalyst uses metal oxide, the metal oxide and CO occurs reduction reaction, generates low valence metal oxide, the reaction temperature is 700 DEG C, the reaction time is 50 minutes. Low valence metal oxide and water vapor occur cracking reaction, regenerate high valence metal oxide and hydrogen, the reaction temperature is 1200 DEG C, the reaction time is 50 minutes, hydrogen occurs synthetic ammonia reaction with nitrogen in ammonia reaction device, generates ammonia, the reaction temperature is 470 DEG C, the reaction time is 50 minutes.

[0059] Example 4:

[0060] A tower type solar energy thermo-chemical ammonia production system and method, the catalyst uses metal oxide, the metal oxide and CO occurs reduction reaction, generates low valence metal oxide, the reaction temperature is 710 DEG C, the reaction time is 60 minutes. Low valence metal oxide and water vapor occur cracking reaction, regenerate high valence metal oxide and hydrogen, the reaction temperature is 1400 DEG C, the reaction time is 60 minutes, hydrogen occurs synthetic ammonia reaction with nitrogen in ammonia reaction device, generates ammonia, the reaction temperature is 500 DEG C, the reaction time is 60 minutes.

[0061] The advantages of the present application are:

[0062] 1. The application adopts chemical cycle heat mode, metal oxides are continuously recycled in the reaction kettle, the consumed raw materials are only carbon substance, water and nitrogen, the process cost is low, through industrial application, the process cost is only 18% of the traditional ammonia production process of coal hydrogen production;

[0063] 2. The application adopts solar energy as a heat source, uses the solar heat collection tower to convert the collected solar energy into heat energy, provides the required heat for the reduction reaction and cracking reaction of the reaction kettle and the CO preparation of the CO reactor, converts the heat energy into chemical energy, and reduces the process energy consumption of the whole ammonia production system;

[0064] 3. The application collects CO2 generated in the reduction reaction in the reaction kettle into the CO reactor to further generate CO, and almost no CO2 emission is generated;

[0065] 4. The application has high energy utilization efficiency, reduces the waste of exhaust heat, and obtains high ammonia production efficiency.

[0066] The above is only the preferred embodiment of the application and is not used to limit the application, for those skilled in the art, the application can have various changes and variations. Any modification, equivalent replacement, improvement, etc. within the spirit and principle of the application shall be included in the protection scope of the application.

Claims

1. A tower-based solar thermochemical ammonia production system, characterized in that, The application relates to a tower type solar heat collecting module, a photo-thermal reaction module and an ammonia production module. The tower type solar heat collecting module comprises a heliostat field and a solar heat collecting tower, the heliostat field reflects sunlight to the solar heat collecting tower, and the collected solar energy is converted into heat energy. The photo-thermal reaction module comprises at least one reaction kettle, a CO reactor, a catalyst sample tank and a water vapor storage tank, the solar heat collecting tower is connected with all the reaction kettles and the CO reactor for providing heat required by the reaction; the CO reactor is connected with all the reaction kettles through a first pressure pump, the catalyst sample tank is connected with all the reaction kettles through a powder particle solid feeder, and the water vapor storage tank is connected with all the reaction kettles through a second pressure pump; in the reaction kettle, high-valence metal oxide delivered by the catalyst sample tank is subjected to a reduction reaction with CO delivered by the CO reactor to obtain low-valence metal oxide and CO2, the CO2 returns to the CO reactor to react with carbon material to generate CO again; then, the low-valence metal oxide is subjected to a cracking reaction with water vapor delivered by the water vapor storage tank to obtain high-valence metal oxide and hydrogen. The ammonia production module comprises an ammonia reaction device and an ammonia collecting device, nitrogen and hydrogen produced by the photo-thermal reaction module enter the ammonia reaction device to perform a synthetic ammonia reaction, and the produced ammonia is delivered to the ammonia collecting device. The heliostat field is composed of a plurality of heliostats surrounding the solar heat collecting tower, the heliostat field focuses sunlight on the solar heat collecting tower, the height and angle of the heliostat are adjusted to control the temperature of the solar heat collecting tower, thereby controlling the heating temperature of the reaction kettle and the CO reactor; the reaction kettle is a solid bed reactor or a boiling bed reactor, and is internally provided with a stirring device.

2. The tower-based solar thermochemical ammonia synthesis system of claim 1, wherein, The high-valence metal oxide is Fe3O4, the low-valence metal oxide is FeO, and the average particle diameter of the high-valence metal oxide and the low-valence metal oxide is between 5-100 um.

3. The tower-based solar thermochemical ammonia production system of claim 1, wherein, In the reaction kettle:

4. The tower-based solar thermochemical ammonia production system of claim 3, wherein, The reaction temperature of the reduction reaction is 680-710 DEG C, and the chemical reaction equation is: Fe3O4+ CO = 3FeO + CO2; The reaction temperature of the cracking reaction is 1000-1400 DEG C, and the chemical reaction equation is: The photo-thermal reaction module further comprises a first condenser, a hydrogen membrane separator, a waste gas storage tank and a hydrogen storage tank. 3FeO + H2O ( l )= Fe3O4 + H2.

5. The tower-based solar thermochemical ammonia production system of claim 1, wherein, A first condenser is connected to the gas outlet of the reaction kettle, the first condenser is used for removing water vapor in high-temperature mixed gas containing hydrogen, the removed water vapor is delivered to the water vapor storage tank through a third pressure pump, the remaining gas after the water vapor is removed enters the hydrogen membrane separator; the purified hydrogen separated through the hydrogen membrane separator is stored in the hydrogen storage tank, the waste gas after the hydrogen is separated is stored in the waste gas storage tank; the hydrogen storage tank is connected with the ammonia reaction device. The ammonia production module further comprises a second condenser, the second condenser is arranged between the ammonia reaction device and the ammonia collecting device, and is used for reducing the temperature of the produced ammonia gas, thereby facilitating collection.

6. The tower solar thermochemical ammonia synthesis system of claim 1, wherein, The application relates to a tower type solar heat collecting module, a photo-thermal reaction module and an ammonia production module.

7. A method of ammonia production based on the tower-based solar thermochemical ammonia production system of claim 5, characterized in that, ​ Step 1, high-valence metal oxide as catalyst is added into the reactor through powder particle solid feeder, and is uniformly stirred to disperse; Open the first pressure pump, and the CO reactor is used to introduce CO gas into the reactor, the temperature of the reactor is controlled at 680-710℃, and reduction reaction occurs, the reaction time is 30-60 min, and after the reaction is completed, the generated CO2 is collected back to the CO reactor; Step 2, close the first pressure pump, open the second pressure pump, and introduce water vapor into the reactor, the temperature of the reactor is controlled at 1000-1400℃, and cracking reaction occurs, the reaction time is 30-60 min, and high-valence metal oxide and hydrogen gas are obtained; Step 3: nitrogen and hydrogen gas prepared in step 2 are introduced into the ammonia reaction device, the temperature of the ammonia reaction device is controlled at 400-500℃, ammonia synthesis reaction occurs, the reaction time is 30-60 min, and the generated ammonia gas is collected in the ammonia collection device.

8. The method of claim 7, wherein the ammonia is produced at a rate of at least 0.1 g / hr. In the step 1, CO2 reacts with carbon material in the CO reactor at 600-800℃ to regenerate CO, realizing the recycling of CO.

9. The method of claim 7, wherein the ammonia is produced at a rate of at least 0.1 g / hr. In the step 2, The mixed gas containing hydrogen generated by cracking reaction is first cooled by the first condenser to remove excess water vapor, the removed water vapor is transported to the water vapor storage tank by the third pressure pump, the remaining gas after removing the water vapor enters the hydrogen membrane separator, the purified hydrogen separated by the hydrogen membrane separator is stored in the hydrogen storage tank, the waste gas after separating hydrogen is stored in the waste gas storage tank, and the hydrogen in the hydrogen storage tank is transported to the ammonia reaction device.

10. The method of claim 9, wherein the ammonia is produced at a rate of at least 0.1 g / hr. In the step 3, The generated ammonia gas is cooled by the second condenser, the remaining gas is treated and discharged, and the ammonia gas is collected by the ammonia collection device.

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